JPS58176178A - Ceramic composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides porcelain compositions that can be sintered at low temperatures, particularly at temperatures below 1050°C, that have high electrical conductivity, high insulation resistance at high temperatures and high temperatures, and low mechanical strength. It concerns a porcelain composition.

Conventionally, as an electric porcelain composition, Balik titanate A (
It is well known that m-devices containing BaTiOs as a main component have been widely put into practical use. However, those whose main component is barium titanate (BaTiOm) have a high sintering temperature of usually 1300 to 1400'C.

Therefore, when this is used in a laminated co/denna, a material that can withstand this sintering temperature must be used as an internal electrode, such as an expensive noble metal such as platinum or palladium, which increases the manufacturing cost F. The drawback is that it is expensive. In order to manufacture multilayer capacitors at low cost, it is necessary to use porcelain that can be sintered at as low a temperature as possible, especially at K 1010'C or less, so that the internal electrodes Km can be made of inexpensive metals mainly composed of silver, nickel, etc.

In addition, the electrical properties of the porcelain composition include a high dielectric constant,
-Basically required is low electrical loss and high insulation resistance. Furthermore, regarding the value of insulation resistance, the US Department of Defense standard that requires reliable parts is Military Specified Case 1 (Military Sp@cifi).
In MIL-C-55681B of CATIOTO+), not only the value at room temperature but also the value at 125°C is specified. , insulation resistance at the maximum operating temperature must also be high.

In addition, in the case of a multilayer chip capacitor, when a real number of chip capacitors are placed on a board, mechanical distortion is added to the chip capacitor tK due to the difference in thermal expansion coefficient K between the board and the porcelain that makes up the chip capacitor. The capacitor may crack or be damaged.

Furthermore, even in the case of a dig condenser coated with epoxy resin or the like, gap condenser tK tack may occur due to the stress of the coat. In either case, the lower the mechanical strength of the porcelain constituting the capacitor, the more likely it is to get stuck in and break, resulting in lower reliability. Therefore, it is of practical importance to increase the mechanical strength of porcelain as much as possible.

By the way, R? I, N, Kraiml
k and m, ■.

Qraatvmksp (Fitike duty r4ege
'r*1a, Tel, 2. A1. pp.

There was a proposal from W ~ n, J Nishikima ara 1%O), and (8rx Pb□, TkOa) 5 (PbIMI0W
ts On) h (however, g=o~aio, @
Ha (135 ~ Q, 5. k 410. S ~ (L66
So, for 6÷b=13, 41Ws@S2 1 is a monolithic condenser and its manufacturing method.
It is disclosed in Japanese Patent Application No. 662, and is also disclosed in Special Issue No. 52-411111 as a Kasumiden experience powder composition.

However, none of them discloses the specific resistance at all, and the practicality of these magnetic S compositions was not clear. In addition, the present inventors can sinter at a temperature of RK910-1150 °C and consist of a binary system of Pb(MyMW%) and PbTi0m, which can be sintered at a temperature of RK910-1150°C, which can be converted into (Pb(M#)On).
We propose a composition in which S is in the range of α65 (z≦1.00) when expressed as s [PbT i Os )1-z. This composition has a high product of dielectric constant and specific resistance, and It has excellent electrical properties with low loss.However, all of the above compositions have low mechanical strength, so their applications have been forced to be limited to a narrow range.

Furthermore, regarding a ternary system including the PboIiI%W3A)Os-PbTiOs system, Fb(M#MWM)01 Pk+Ti0m
Pb(M#MNbX)On system is specially Ill@51i
-117809 Pb (Ima store) 0. -PbTi
Okarasu-3% (M#MTIL) On series are disclosed, respectively. However, none of them discloses specific resistance or mechanical strength, and the practicality of these ceramic compositions was not clear.

In addition, the inventors have determined that RKi% (in k11 garden) 0 attack-Pb
A T1 pseudo-P b (to Nt3fNk) Oa ternary composition is proposed.

This O composition can be sintered in the low temperature range of 900 to 1050°C, has excellent properties such as high dielectric constant, low electrical loss, and high insulation resistance values at room temperature and high temperature.

However, due to the low mechanical strength of the composition, its use had to be limited to a narrow range.

In view of the above points, the present invention can be sintered in a low temperature range of 900 to 1050°C, has a high dielectric constant, and has a low sieving loss.
The purpose is to provide a highly reliable porcelain composition that has excellent electrical properties such as high insulation resistance values at room temperature and high temperature, and also has high mechanical strength. )fW%)Os)
3 consisting of p-lead titanate (PbTiOm) and lead niobate (Pb (Ni to 'Nb) 0 [present]]
The luminous composition (Pb Oa#bright%)Os ) z (P
bT iOs )y CPb (Ni%Nb%)]1
(however, earthquake + 10 g, =
g=α01)j(g=Q, 495, y=o,
41s, g=ao1) (g=0.19!
, y=0.455, g-0,35) (5=
alO, y-0,40, g=O56) (g=006
, y=α24, g=α70)(Pb(Mm3
48b
It is characterized by containing l-addition.

Hereinafter, the present invention will be explained in detail with reference to Examples.

Lead oxide (PbO) with a purity of 99.9 or higher as a starting material
.

Magnesium oxide (hILJO), tungsten oxide (
%VOs) pTitanium oxide (Tilt), nickel oxide (NIO), 11 and niobium oxide (NbsOi)*
Antimony oxide (8bsOs>) and manganese oxide (l
hcOl) and weigh each to achieve the blending ratio shown in the table. Next, the weighed materials were wet-mixed in a ball gill, then pre-baked at 750~$0.00. This powder was crushed with a 4-ball ball, divided into sieves, dried, and an organic binder was added. 14 disks each having a diameter of 165 wm and a thickness of approximately 2 m, and a cylinder having a diameter of 165 wm and a thickness of approximately IDwx were prepared using a V-shaped tube.

Next, a sample having a composition in the composition range of the present invention was sintered in air at a temperature of 10 mm for 1 hour. At the top and bottom m of four sintered disks @
Burn the silver electrode with oo'c, digital LCR meter frequency 1 iQh, voltage "Vr, &I.

The capacitance and dielectric loss were measured at a temperature of 120° C., and the dielectric constant was calculated.

Next, apply a voltage of 50V for 1 minute with a super-insulated resistance needle,
Insulation resistance was measured at elevated temperatures and at 125°C, and specific resistance was calculated.

In order to evaluate the bending strength of mechanical properties, a sintered cylinder with a thickness Q, S m , @ 2 wx and a length of about 13
I cut out w pieces of 1oK rectangular board. The distance between the fulcrums is 9 x
s Ic taken Pwl Measure the breaking load hO by the two-point method, y m7-; π-4
], the bending strength τ [force-] was determined. However, l is the distance between the supporting points, t is the thickness of the sample, and 2w is the width of the sample. The electrical properties were determined from the average value of four disk samples.The bending strength was determined from the average value of point W of the rectangular plate sample.

The main components of the porcelain (PM-Os), (pbttom), (
pb (Ntxx%)] 1 metal distribution ratio, y, 1 and the additive amount of subcomponents, dielectric constant, dielectric loss, 20°C and 12S
The relationship between specific resistance at t K and bending strength is shown in the following table.

Table V - From the results shown, the beak 5%, Pb--W%)
01- PblTi0m Pki(NiMNk+X)O
Pb (lh%81e
Those within the scope of the present invention that contain X)On are:
The dielectric constant is 2950-12960 and the dielectric loss is 0.3.
It is as small as ~28-, and the specific resistance is ztKmitetxXl0
L1.7 xICIsn-cxstrls<#t, 4. OX to'-: a, s
It can be seen that this is a highly reliable and extremely practical porcelain composition that exhibits a high value of xlo'Ω''C1l, and also has a bending strength of 98 to 1410, which is a sufficiently high value for practical use.

The porcelain of the present invention exhibiting these excellent properties has a sintering temperature of 1
Since the temperature is low, below 0.050°C, it is possible to reduce the cost of the internal electrodes of the laminated pundenna, and it also has extremely excellent effects such as saving energy and saving furnace materials.

In addition, the main component composition of the present invention (PB information-Mls)
g (PbTl false) y (PMNi to pigeon) When expressed as Os3g, k (however, # s + y ten liao = 1.00),
Its composition is shown at the bottom point (s=0.693, y=Q, 2117,
g = = co, ol ) (x = o, 49s, y;
a4Gs, g=ao1) (gxQ, 11s
, y=α40, $=035) (g=alo
, y=040, g=050 ) (1gwαO@
, yx (124,!=α7G) and the composition range surrounded by this point s is limited to the composition range HK, and the added content of the 111 component is (LO5-6 Otori・1% E
ll determined. 3 components representing the main component composition range 1
1 Kk, and outside the line connecting composition points 2 and 6 and composition point 17.19, the specific resistance becomes small at high temperatures, making it impractical. Outside the line connecting the composition points @, 13, and 17, the +1 point deviates significantly from the practical range, so #I dielectric constant becomes smaller, and outside the line connecting the composition points 1 and 2, it becomes KI.

Since the point deviates significantly to the lower temperature side than the practical range, the electrical power becomes small, making it impractical.

In addition, when the amount of Pb (&sb) Os added as a subcomponent is 0 and less than Oram 19A, the improvement effect of bending strength Ikf
If it exceeds .ml-, the bending strength will decrease, which is not practical.

In addition, the main component composition range of the main component of liK is shown. The numbers shown in the figure correspond to the numbers of the main component blending ratios shown in the table.

[Brief explanation of the drawing]

The figure is a diagram showing the principal component composition range of the invention and the composition points shown in the example. Pb (A/i Nb yoke) 03 Pb (M13hWq) 0. P
bTt'O. Procedural Amendment (Toge) Director General of the Patent Office 1, Indication of the Case 1981 Application No. osg
SSS No. 2, Name of the invention Magnetic MS Composition 3, Relationship with the amended case Applicant No. 33-1 (423) Shiba Go, Minato-ku, Tokyo NEC Corporation Representative Tadahiro Sekimoto 4 , Agent Address: 5, Sumitomo Sanda Building, 37-8 Shibago, Minato-ku, Tokyo 108, Detailed explanation of the invention in the specification subject to amendment 6 Contents of the amendment Line 14 of the 4th page of the specification "a -' = b J" is corrected to "a + b J," Patent Attorney Uchihara ￥!f13

Claims (1)

[Claims] Magnesium lead tungstate (Pb (MyMWM)
On) P lead titanate (PbTiO, ) and nickel lead niobate (Pb (NhNb%)Os) 3
The component composition is (Pb (Hatoichi W%)Os) z (Pb
T i Os ) y (Pb (N hNk+X )
On) When expressed as g, (however, g+y+g-1
,00) In this ternary component diagram, the following composition points (sneOJI3, y=(L217,
g=ao1)(&+trimα495, jeQ,
411! s, g=(LOI)(gmo, 1
11! , y=t(k, 451!, s=
α35) ($=*o, 10, j=0.40
, gz(LSO)(sxooe # y=a
z4, g=ayo)
Manganese-an + lead soyate (PM & Jals
) as a main component, and the addition of TEQ, 01S to @M1alIs to make the bone mold a porcelain composition.